US2894014A - Complex esters of beta-phosphato-alpha, beta-olefinically unsaturated monocarboxylic acids - Google Patents
Complex esters of beta-phosphato-alpha, beta-olefinically unsaturated monocarboxylic acids Download PDFInfo
- Publication number
- US2894014A US2894014A US555753A US55575355A US2894014A US 2894014 A US2894014 A US 2894014A US 555753 A US555753 A US 555753A US 55575355 A US55575355 A US 55575355A US 2894014 A US2894014 A US 2894014A
- Authority
- US
- United States
- Prior art keywords
- group
- beta
- groups
- carbon atoms
- phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 150000002148 esters Chemical class 0.000 title description 15
- 150000002763 monocarboxylic acids Chemical class 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 description 25
- 125000004432 carbon atom Chemical group C* 0.000 description 24
- -1 hydrocarbyl alcohol Chemical compound 0.000 description 23
- 239000000047 product Substances 0.000 description 19
- 241000238631 Hexapoda Species 0.000 description 15
- 125000000524 functional group Chemical group 0.000 description 14
- 229910019142 PO4 Inorganic materials 0.000 description 13
- 239000002917 insecticide Substances 0.000 description 13
- 235000021317 phosphate Nutrition 0.000 description 13
- 231100000419 toxicity Toxicity 0.000 description 13
- 230000001988 toxicity Effects 0.000 description 13
- 239000010452 phosphate Substances 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 11
- LCCNCVORNKJIRZ-UHFFFAOYSA-N parathion Chemical compound CCOP(=S)(OCC)OC1=CC=C([N+]([O-])=O)C=C1 LCCNCVORNKJIRZ-UHFFFAOYSA-N 0.000 description 10
- 238000005507 spraying Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 206010061217 Infestation Diseases 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- BIWJNBZANLAXMG-IDTQJTQFSA-N cis-chlordane Chemical compound ClC1=C(Cl)[C@@]2(Cl)[C@@H]3C[C@@H](Cl)[C@@H](Cl)[C@@H]3[C@]1(Cl)C2(Cl)Cl BIWJNBZANLAXMG-IDTQJTQFSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 3
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 3
- 241000462639 Epilachna varivestis Species 0.000 description 3
- 244000267823 Hydrangea macrophylla Species 0.000 description 3
- 235000014486 Hydrangea macrophylla Nutrition 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 241001454293 Tetranychus urticae Species 0.000 description 3
- 241000607479 Yersinia pestis Species 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001348 alkyl chlorides Chemical class 0.000 description 3
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 229960003750 ethyl chloride Drugs 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 230000000749 insecticidal effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- SNICXCGAKADSCV-JTQLQIEISA-N (-)-Nicotine Chemical compound CN1CCC[C@H]1C1=CC=CN=C1 SNICXCGAKADSCV-JTQLQIEISA-N 0.000 description 2
- 241000238876 Acari Species 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000253994 Acyrthosiphon pisum Species 0.000 description 2
- 241001425390 Aphis fabae Species 0.000 description 2
- 241001600408 Aphis gossypii Species 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 241001414720 Cicadellidae Species 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 241000257159 Musca domestica Species 0.000 description 2
- 241000721621 Myzus persicae Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 241001521235 Spodoptera eridania Species 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- DFBKLUNHFCTMDC-PICURKEMSA-N dieldrin Chemical compound C([C@H]1[C@H]2[C@@]3(Cl)C(Cl)=C([C@]([C@H]22)(Cl)C3(Cl)Cl)Cl)[C@H]2[C@@H]2[C@H]1O2 DFBKLUNHFCTMDC-PICURKEMSA-N 0.000 description 2
- 229950006824 dieldrin Drugs 0.000 description 2
- NGPMUTDCEIKKFM-UHFFFAOYSA-N dieldrin Natural products CC1=C(Cl)C2(Cl)C3C4CC(C5OC45)C3C1(Cl)C2(Cl)Cl NGPMUTDCEIKKFM-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013601 eggs Nutrition 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229960002715 nicotine Drugs 0.000 description 2
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Natural products CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- GZPINROYMLOPBI-UHFFFAOYSA-N 2-acetyloxyethyl 2-chloro-3-oxobutanoate Chemical compound ClC(C(=O)OCCOC(C)=O)C(=O)C GZPINROYMLOPBI-UHFFFAOYSA-N 0.000 description 1
- WNYYNLLSCINXBT-UHFFFAOYSA-N 2-acetyloxyethyl 3-dimethoxyphosphoryloxybut-2-enoate Chemical compound P(=O)(OC(=CC(=O)OCCOC(C)=O)C)(OC)OC WNYYNLLSCINXBT-UHFFFAOYSA-N 0.000 description 1
- NGAVSCAXDJMZQP-UHFFFAOYSA-N 2-acetyloxyethyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OCCOC(C)=O NGAVSCAXDJMZQP-UHFFFAOYSA-N 0.000 description 1
- VCBFAUSKNYAKJZ-UHFFFAOYSA-N 2-chloro-3-oxobutanoic acid Chemical compound CC(=O)C(Cl)C(O)=O VCBFAUSKNYAKJZ-UHFFFAOYSA-N 0.000 description 1
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 description 1
- KXWQPGYHAZORFX-UHFFFAOYSA-N 2-methoxyethyl 2-chloro-3-oxobutanoate Chemical compound COCCOC(=O)C(Cl)C(C)=O KXWQPGYHAZORFX-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- 241001124076 Aphididae Species 0.000 description 1
- 241000239290 Araneae Species 0.000 description 1
- 241000238421 Arthropoda Species 0.000 description 1
- OKTJSMMVPCPJKN-IGMARMGPSA-N Carbon-12 Chemical group [12C] OKTJSMMVPCPJKN-IGMARMGPSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000254173 Coleoptera Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- YVGGHNCTFXOJCH-UHFFFAOYSA-N DDT Chemical compound C1=CC(Cl)=CC=C1C(C(Cl)(Cl)Cl)C1=CC=C(Cl)C=C1 YVGGHNCTFXOJCH-UHFFFAOYSA-N 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- 241001515686 Erythroneura Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 241000500891 Insecta Species 0.000 description 1
- 241000721715 Macrosiphum Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000131095 Oniscidea Species 0.000 description 1
- 239000005950 Oxamyl Substances 0.000 description 1
- 241001480169 Phaseolus maculatus Species 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- RZKYEQDPDZUERB-UHFFFAOYSA-N Pindone Chemical group C1=CC=C2C(=O)C(C(=O)C(C)(C)C)C(=O)C2=C1 RZKYEQDPDZUERB-UHFFFAOYSA-N 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 241001163248 Schoenocaulon officinale Species 0.000 description 1
- IDCBOTIENDVCBQ-UHFFFAOYSA-N TEPP Chemical compound CCOP(=O)(OCC)OP(=O)(OCC)OCC IDCBOTIENDVCBQ-UHFFFAOYSA-N 0.000 description 1
- 241001454294 Tetranychus Species 0.000 description 1
- 241000339374 Thrips tabaci Species 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 241000251539 Vertebrata <Metazoa> Species 0.000 description 1
- 241000219094 Vitaceae Species 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 125000001980 alanyl group Chemical group 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000012550 audit Methods 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- BUBXMFDYDWDNGT-UHFFFAOYSA-N diethyl 2-methoxyethyl phosphate Chemical compound CCOP(=O)(OCC)OCCOC BUBXMFDYDWDNGT-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- JEVDMRPLYXRCKV-UHFFFAOYSA-N diethyl prop-1-enyl phosphate Chemical compound CCOP(=O)(OCC)OC=CC JEVDMRPLYXRCKV-UHFFFAOYSA-N 0.000 description 1
- IFICZGJOMDVWLV-UHFFFAOYSA-N dimethyl prop-1-enyl phosphate Chemical compound COP(=O)(OC)OC=CC IFICZGJOMDVWLV-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- ZUNGGJHBMLMRFJ-UHFFFAOYSA-O ethoxy-hydroxy-oxophosphanium Chemical compound CCO[P+](O)=O ZUNGGJHBMLMRFJ-UHFFFAOYSA-O 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- GEHREXOPBQKODZ-UHFFFAOYSA-N ethyl 2-methoxyethyl hydrogen phosphate Chemical compound CCOP(=O)(O)OCCOC GEHREXOPBQKODZ-UHFFFAOYSA-N 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 125000000350 glycoloyl group Chemical group O=C([*])C([H])([H])O[H] 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 235000021021 grapes Nutrition 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- QPPQHRDVPBTVEV-UHFFFAOYSA-N isopropyl dihydrogen phosphate Chemical compound CC(C)OP(O)(O)=O QPPQHRDVPBTVEV-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 229940059904 light mineral oil Drugs 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- KZAUOCCYDRDERY-UHFFFAOYSA-N oxamyl Chemical group CNC(=O)ON=C(SC)C(=O)N(C)C KZAUOCCYDRDERY-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- XFKRSSJJDQIILX-UHFFFAOYSA-N prop-1-enyl dihydrogen phosphate Chemical compound CC=COP(O)(O)=O XFKRSSJJDQIILX-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229940080817 rotenone Drugs 0.000 description 1
- JUVIOZPCNVVQFO-UHFFFAOYSA-N rotenone Natural products O1C2=C3CC(C(C)=C)OC3=CC=C2C(=O)C2C1COC1=C2C=C(OC)C(OC)=C1 JUVIOZPCNVVQFO-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 235000017709 saponins Nutrition 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- ARZWPIKXHHNGCT-UHFFFAOYSA-N tris(2-methoxyethyl) phosphite Chemical compound COCCOP(OCCOC)OCCOC ARZWPIKXHHNGCT-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N γ Benzene hexachloride Chemical compound ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/113—Esters of phosphoric acids with unsaturated acyclic alcohols
Definitions
- This invention relates to a new class of phosphoruscontaining compounds which have been found to be particularly useful as insecticides.
- the compounds of the invention are esters of betaphosphato alpha,beta-olefinically unsaturated monocarboxylic acids represented by the formula wherein R represents a hydrogen atom or a hydrocarbon radical, with an aliphatic alcohol which contains at least one other functional group containing oxygen.
- the esters of the invention thus include esters of the acid of the said structure wherein one, two, or all three of the acidic hydrogen atoms are replaced by the residue of the said aliphatic alcohol. Where less than all of the acidic hydrogen atoms are replaced by the residue of the said alcohol, it is preferred that the remaining acidic hydrogen atom or atoms be replaced by the residue of a hydrocarbyl alcohol, ROH, wherein R represents a hydrocarbyl group asset out hereinafter.
- the aliphatic alcohol containing an additional oxygen-containing functional group may be considered to have the formula: HOR R wherein R represents a divalent aliphatic hydrocarbon group and R represents a functional group involving oxygen. Accordingly, the compounds of the invention may be generically represented by the formula:
- R represent either a hydrogen atom or a hydrocarbon ,group containing from 1 to about 8 carbon atoms.
- R thus includes aliphatic-including cycloaliphatichydrocarbon groups, such as alkyl groups of either straight-chain or branchedchain configuration, cycloalkyl groups, and their unsaturated analogs, aryl groups, and combinations thereof, such as araliphatic groups and aryl groups substituted by one or more aliphatic groups, e.g., aralkyl and alkaryl groups.
- such groups contain not more than about eight carbon atoms each, considering both ring and nonring carbon atoms. It is preferred that R be an alkyl group, the lower alkyl groups, those containing 8 carbon atoms or less, each being the most desirable.
- the symbol R represents the same hydrocarbon groups as are designated by the symbol R.
- R represents a divalent aliphatic hydrocarbon radical, the linking valence bonds being on the same or on different carbon atoms. These groups may be of either straight-chain or branched chain configura- States Patent 0 ice tion. It is preferred that R represent'an alkylene group, anclthat the group contain not more than about ten carbon atoms.
- R represents a functional group involving oxygen--by which term is meant any reactive functional group which includes an oxygen atom.
- groups include the 'hydroxyl group, --OH; the ether group -OR*; the carboxy group, -C(O)OH, and ester groups, -C(O)OR such as the carboalkoxy groups derived from glycolic acid, lactic acid, and like hydroxycarboxylic acids, and the R esters thereof; carbonyl groups, such as the aldehyde group, --C(O )H, and ketone groups, C(O)R including such groups as the acetyl group, the benzoyl group, the anisoyl group, caproyl group, and the like, olefinically unsaturated groups such as the acrylyl group, the crotonyl group, and the like, and such substituted groups as the alanyl group, the anthranoyl group, the benziloyl group, the oxamyl group
- R aso represents such groups as the sulfonic acid group, SO H, and esters thereof, -SO R the nitro group, -NO the nitroso group, --ONO; the carbamyl group, H NC(O)- and the R derivatives thereof, and the like. Also included within the meaning of R are hydrocarbon groups linked to the group R through an oxygen-containing functional group and also such groups containing one or more additional oxygen-containing functional groups, such as the acyloxy groups, --OC(O)R the acetoxy group, the benzoyloxy group, the pivalyloxy group, and the like.
- More than one group R may be substituted on the group R
- the functional groups represented by R be composed of atoms selected from the group consisting of carbon, hydrogen and oxygen atoms.
- R represents the groups defined by the symbol R. It is preferred that the groups designated by R contain not more than about 10 carbon atoms each, including the carbon atoms contained in the groups designated as R
- the preferred compounds of the invention are the esters of aliphatic polyhydric alcohols, especially glycols, and derivatives thereof such as esters or ethers of such alcohols.
- esters are conveniently prepared by (a) ester interchange between an alcohol or phenol having an oxygen-containing functional group (R R OH) or, in the case of compounds of the type represented by Formula III, a simple hydrocarbyl alcohol, (ROH), with an ester of a hydrocarbyl-substituted beta-0x0 fatty acid, R'C(O)CHR'-C(O)-OR", according to the equation:
- hydrocarbyl substituted beta-0x0 fatty acids are well known and are generally prepared according to the method described by Bader et al., Journal of the American Chemical Society, volume 73, pages 4195-7 (1951). This reference also sets out the method for conducting Reaction a.
- the phosphites ((RO) P, (R R O) P) are a well known class of compounds ordinarily prepared by reacting one mole of phosphorus trichloride with three moles of an alcohol (ROH, R R OH) in the presence of three moles of a basic hydrogen chloride acceptor such as pyridine or trimethylamine.
- the phosphites- (RO),,(R R O);',P are prepared in a similar manner by first reacting one mole of phosphorus trichloride with a moles of the alcohol ROH and a moles of the hydrogen chloride acceptor and then reacting the product with b moles of the alcohol R R OH with b moles of the hydrogen chloride acceptor.
- Reaction c is carried out by adding about an equimolar amount of the phosphite to the chloroester, the addition usually being made slowly so as to avoid undue temperature increase of the reaction mixture from the exothermic heat of reaction.
- the reaction may be started with the reactants at an ordinary temperature of about to C., but for the most part is conducted at a temperature between about 60 C. and 150 C. In some cases, the starting of the reaction is assisted by applica tion of heat, and especially if large quantities of reactants are used, cooling is employed to control the temperature within the desired range.
- the formed alkyl chloride is preferably removed from the reaction mixture to greater or lesser extent by application of suflicient vacuum so the chloride is boiled out.
- reaction is catalyzed by acidic or basic catalysts, such as acid or basic resins, tertiary amines, or sulfonic acids.
- acidic or basic catalysts such as acid or basic resins, tertiary amines, or sulfonic acids.
- the reaction is conveniently effected by heating a mixture of approximately equimolar portions of the diketene and the alcohol, together with a catalytic amount of the catalyst, to a moderately elevated temperature (100 C. to 150 C. is usually most satisfactory) for a suflicient time to complete the reaction.
- a resin is used as catalyst it is then removed by filtration, and the product obtained by distillation of the filtrate.
- an amine or sulfonic acid is used as catalyst, it may be removed by neutralization and/or washing the reaction mixture with water, followed by drying of the product and removal of the solvent. This reaction is illustrated by the following example:
- EXAMPLE I Reaction of an alcohol with diketene 2-acetoxyethyl acetoacetate is prepared by mixing diketene (42 grams-05 mole) and 2-hydroxyethyl acetate (52 grams0.5 mole) together with 1 gram of a sulfonic acid ion exchange resin (Amberlite IR-120, acid form) and heating carefully at to C. for approximately 1 hour. The resin is removed by filtration.
- a sulfonic acid ion exchange resin Amberlite IR-120, acid form
- the complex esters of the invention are liquids at ordinary temperatures of C. to C. although higher members are crystalline solids at such normal temperatures.
- the new compounds are very useful substances for a variety of applications but are of particular utility as insecticides because they possess outstanding properties when employed ascontact and stomach poi sons.
- the compounds are highly toxic to insects, a term which is employed herein to include not only members of the class Insecta, but also related or similar non-vertebrate animal organisms belonging to the allied classes of arthropods and including mites, ticks, spiders, wood lice, and the like.
- the compounds of this invention can be employed for insecticidal purposes by the use of any of the methods which are conventionally employed in that art.
- the compounds can either be sprayed or otherwise applied in the form of a solution or dispersion, or
- Useful solutions for. application by spraying, brushing, dipping, and the like, can be prepared by using as the solvent any of the well-known inert horticultural carriers, including neutral hydrocarbons such as kerosene and other light mineral oil distillates of intermediate viscosity and volatility.
- Adjuvants such as spreading or wetting agents, can also be included in the solutions, representative materials of'this character being fatty acid soaps, rosin 'salts, saponins,' gelatin, casein, long-chain fatty alcohols, alkyl aryl sulfonates, long-chain alkyl sulfonates, phenolethylene oxide condensates, ammonium salts, and the like.
- These solutions can be employed as such, or, more preferably, they can be dispersed or emulsified'in' water and the resulting aqueous dispersion or emulsion applied as a spray.
- Solid carrier materials which can be employed include talc, bentonite, lime, gypsum, pyrophyllite andsimilar inert solid ,dilu'ents.
- the compounds of the present invention can be employed as aerosols, as by dispersing the same into the atmosphere by means of a compressed
- concentration of the compounds to be used with the above carriers is dependent upon many factors, including the particular compound utilized, the can'ier employed, the method and conditions of application, and the insect speciesto be controlled, a proper consideration and resolution of these factors being within the skill of those versed in the insecticide art.
- the compounds of this invention are effective in concentrations of from about 0.01% to 0.5% based upon the total weight of the composition, though under some circumstances as little as about 0.00001% or as much as 2% or even more of the compound can be employed with good results from an'in'secticidal standpoint.
- a compound of this invention When employed as an insecticide, a compound of this invention can be employed either as the: sole toxic ingredient of the insecticidal composition or can be employed in conjunction with otherinsecticidallkactive materials.
- Representative insecticides of this latter class include the natura yoc unin i se cides such as. .py-
- EXAMPLE X In furthertests, representative compounds of the invention were tested against other common insect pests, comparison being made to common insecticides widely used'against such pests. Solutions or emulsions of the representative compounds were made up by employing acetone, or a neutral petroleum distillate lying within the kerosense range as the solvent.
- D 2- 2-(benzoyloxy)ethoxycarbonyl]-1-methylvinyl dlmethyl phosphate.
- E 2-carbethoxy-1-methylvinyl ethyl 2-methoxyethyl phosphate.
- F 2-(2-methoxyethoxycarbonyl)-1-methylvinyl diethyl phosphate.
- G Bls-(2-methoxyethyl) 2-(2-methoxyeth0xyoarbonyl)-1methylviny1 phosphate.
- Certain representative compounds of the invention were tested to determine their residual toxicity with respect Percent control to the adults of several common insects. These tests were pe'rfiormediby spraying the unifested test plants with the Concentration of active materialinspray.-. 1.0% w. 0.25% w. test compound as set out in Example IX, and a given I y p j number of days thereafter infesting the plantswith the Time (infestation after spraying, days) 1 7 1 7 testinsects. The effectiveness of the test compound is expressed as the percent of the test insects (compared to oomnzund i m 100 100 99 51 S68 8, e c.
- the Young hatched Concentration ractive'mater a in spr i 0 g -l from the eggs, as well as the adults of two-spotted spider mites, would be measured.
- the time of infestation was Time (infestation after spraying, -deys)... 1 2 7 7 days after spraying.
- the results are shown in the folr lowing table. (In the table, the concentration of the Percent n 100 100 78 test compound in the spray is given in parentheses following the percent kill.)
- R represents a member of the group consisting of hydrogen and alkyl radicals of 1 to 8 carbon atoms
- R represents an alkyl radical of 1 to 8 carbon atoms
- R represents an alkylene group of not more than 10 carbon atoms
- R represents a functional group involving oxygen of not more than 10 carbon atoms selected from the group consisting of -0R and wherein R represents a member of the group consisting of hydrogen and alkyl radicals of 1 to 8 carbon- 12 atoms
- R represents an alkyl radical of 1 to 8 carbon atoms
- R represents a functional group involving oxygen of not more than 10 carbon atoms selected from the group consisting of OR and wherein R is an alkyl radical.
- R represents a member of the group consisting of hydrogen and alkyl groups of 1 to 8 carbon atoms
- R represents an alkyl radical of 1 to 8 carbon atoms
- R represents an alkylene group of not more than 10 carbon atoms
- R represents a functional group involving oxygen of not more than 10 carbon atoms selected from the group consisting of --OR and wherein R is an alkyl radical.
- R represents a member of the groupconsisting of hydrogen and alkyl radicals to 1 to 8 carbon atoms
- R represents an alkyl radical of 1 to 8 carbon atoms
- R3 represents an alkylene group of not more than 10 carbon atoms
- R represents a functional group involving oxygen having not more than 10 carbon atoms selected from the group consisting of OR and wherein R is an alkyl radical
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Dentistry (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
CQMPLEX ESTERS F BETA-PHOSPHATO-ALPHA,
BETA-OLEFINICALLY UNSATURATED MONO- CARBOXYLIC ACIDS Alan R. Stiles and Richard R. Whetstone, Denver, (3010., assignors to Shell Development Company, New York, N.Y., a corporation of Delaware No Drawing. Application December 28, 1955 Serial No. 555,753
11 Claims. (Cl. 260-461) This invention relates to a new class of phosphoruscontaining compounds which have been found to be particularly useful as insecticides.
The compounds of the invention are esters of betaphosphato alpha,beta-olefinically unsaturated monocarboxylic acids represented by the formula wherein R represents a hydrogen atom or a hydrocarbon radical, with an aliphatic alcohol which contains at least one other functional group containing oxygen. The esters of the invention thus include esters of the acid of the said structure wherein one, two, or all three of the acidic hydrogen atoms are replaced by the residue of the said aliphatic alcohol. Where less than all of the acidic hydrogen atoms are replaced by the residue of the said alcohol, it is preferred that the remaining acidic hydrogen atom or atoms be replaced by the residue of a hydrocarbyl alcohol, ROH, wherein R represents a hydrocarbyl group asset out hereinafter. The aliphatic alcohol containing an additional oxygen-containing functional group may be considered to have the formula: HOR R wherein R represents a divalent aliphatic hydrocarbon group and R represents a functional group involving oxygen. Accordingly, the compounds of the invention may be generically represented by the formula:
wherein R, R, R and R have the meanings set out hereinbefore, a is an integer of from 0 to 2, with the proviso that a+b=2, and c is an integer from 0 to l, with the proviso that c+d=l and b +d=at least 1 and not more than 3.
In these compounds, it is preferred that R represent either a hydrogen atom or a hydrocarbon ,group containing from 1 to about 8 carbon atoms. R thus includes aliphatic-including cycloaliphatichydrocarbon groups, such as alkyl groups of either straight-chain or branchedchain configuration, cycloalkyl groups, and their unsaturated analogs, aryl groups, and combinations thereof, such as araliphatic groups and aryl groups substituted by one or more aliphatic groups, e.g., aralkyl and alkaryl groups. Preferably, such groups contain not more than about eight carbon atoms each, considering both ring and nonring carbon atoms. It is preferred that R be an alkyl group, the lower alkyl groups, those containing 8 carbon atoms or less, each being the most desirable.
The symbol R represents the same hydrocarbon groups as are designated by the symbol R.
The symbol R represents a divalent aliphatic hydrocarbon radical, the linking valence bonds being on the same or on different carbon atoms. These groups may be of either straight-chain or branched chain configura- States Patent 0 ice tion. It is preferred that R represent'an alkylene group, anclthat the group contain not more than about ten carbon atoms.
The symbol R represents a functional group involving oxygen--by which term is meant any reactive functional group which includes an oxygen atom. Examples of such groups include the 'hydroxyl group, --OH; the ether group -OR*; the carboxy group, -C(O)OH, and ester groups, -C(O)OR such as the carboalkoxy groups derived from glycolic acid, lactic acid, and like hydroxycarboxylic acids, and the R esters thereof; carbonyl groups, such as the aldehyde group, --C(O )H, and ketone groups, C(O)R including such groups as the acetyl group, the benzoyl group, the anisoyl group, caproyl group, and the like, olefinically unsaturated groups such as the acrylyl group, the crotonyl group, and the like, and such substituted groups as the alanyl group, the anthranoyl group, the benziloyl group, the oxamyl group, and the like; also included are such groups as the pivalyl group, the alkoxalyl group, the 'glycolyl group, the glyoxylyl group, and the like. R aso represents such groups as the sulfonic acid group, SO H, and esters thereof, -SO R the nitro group, -NO the nitroso group, --ONO; the carbamyl group, H NC(O)- and the R derivatives thereof, and the like. Also included within the meaning of R are hydrocarbon groups linked to the group R through an oxygen-containing functional group and also such groups containing one or more additional oxygen-containing functional groups, such as the acyloxy groups, --OC(O)R the acetoxy group, the benzoyloxy group, the pivalyloxy group, and the like. More than one group R may be substituted on the group R It is preferred that the functional groups represented by R be composed of atoms selected from the group consisting of carbon, hydrogen and oxygen atoms. In these functional groups, R represents the groups defined by the symbol R. It is preferred that the groups designated by R contain not more than about 10 carbon atoms each, including the carbon atoms contained in the groups designated as R The preferred compounds of the invention are the esters of aliphatic polyhydric alcohols, especially glycols, and derivatives thereof such as esters or ethers of such alcohols.
Examples of this new class of esters include:
2 (2 acetoxyethoxycarbonyl) 1 methylvinyl dimethyl phosphate,
2 (2 acetoxyethoxycarbonyl) 1 methylvinyl diethyl phosphate,
2 (2 methoxypropoxycarbonyl) 1 methylvinyl dimethyl phosphate,
2 (2 carboethoxyethoxycarbonyl) l methylvinyl dimethyl phosphate 2 (2 benzoyloxy)ethoxycarbonyl) l methylvinyl dimethyl phosphate Bis(2 methoxyethyl) 2 (2 methoxyethoxycarbonyl)-1-methylvinyl phosphate 2-catrlbethoxy-1-methylvinyl ethyl Z-methoxyethyl phosp ate 2 (3 carbethoxypropoxycarbonyl) 1,2 dimethylvinyl dibutyl phosphate 2 (2 carbobutoxybutoxycarbonyl) 1 ethylvinyl dip'entyl phosphate 2 (2 butoxybutoxycarbonyl) 1 phenylvinyl di isopropyl phosphate phate 2-acetoxycthyl 2-ca rbethoxy-1-methy1vinyl methyl phosphate 2-(Z-acetoxyethoxycarbonyl) ethenyl dirnethyl phosphate Within the generic class of compounds of this invention two subgenera' are of particular utility as insecticides. Compounds of the general Formula I, in which d=1 and a=2, i.e., compounds of the formula R R 0 1i I (R0): O OOO-R1RI (II) in which each of the groups, R, R', R and R contain six carbon atoms or less, have been found to be highly active insecticides with excellent residual activity. Compounds of thegeneral Formula I, wherein 0:1 and b=1 or 2, i.e., compounds of the formula wherein a+b=2 and b=1 or 2, have been found to be highly active against a number of common insect pests. These two subgenera therefore form the preferred aspects of the invention.
These new esters are conveniently prepared by (a) ester interchange between an alcohol or phenol having an oxygen-containing functional group (R R OH) or, in the case of compounds of the type represented by Formula III, a simple hydrocarbyl alcohol, (ROH), with an ester of a hydrocarbyl-substituted beta-0x0 fatty acid, R'C(O)CHR'-C(O)-OR", according to the equation:
The hydrocarbyl substituted beta-0x0 fatty acids are well known and are generally prepared according to the method described by Bader et al., Journal of the American Chemical Society, volume 73, pages 4195-7 (1951). This reference also sets out the method for conducting Reaction a.
(b) Reaction of the product of (a) with sulfuryl chloride to give the 2-chloro-substituted compound wherein a+b=2, and a=0, 1 or 2, to give the desired products. In the reactions set out above, R normally is an alkyl group.
The phosphites ((RO) P, (R R O) P) are a well known class of compounds ordinarily prepared by reacting one mole of phosphorus trichloride with three moles of an alcohol (ROH, R R OH) in the presence of three moles of a basic hydrogen chloride acceptor such as pyridine or trimethylamine. The phosphites- (RO),,(R R O);',P, are prepared in a similar manner by first reacting one mole of phosphorus trichloride with a moles of the alcohol ROH and a moles of the hydrogen chloride acceptor and then reacting the product with b moles of the alcohol R R OH with b moles of the hydrogen chloride acceptor. (Kosolapofi, Organic-phosphorus Compounds, Wiley (1950), pages 184 and 185.)
Reaction c is carried out by adding about an equimolar amount of the phosphite to the chloroester, the addition usually being made slowly so as to avoid undue temperature increase of the reaction mixture from the exothermic heat of reaction. The reaction may be started with the reactants at an ordinary temperature of about to C., but for the most part is conducted at a temperature between about 60 C. and 150 C. In some cases, the starting of the reaction is assisted by applica tion of heat, and especially if large quantities of reactants are used, cooling is employed to control the temperature within the desired range. The formed alkyl chloride is preferably removed from the reaction mixture to greater or lesser extent by application of suflicient vacuum so the chloride is boiled out. When the boiling points of the formed alkyl chloride and the chloroester reactant are fairly close together, use of a distillation column for removal of the alkyl chloride is advisable for best results. Some of the higher reactants are solids at ordinary temperature, but use of an inert solvent such as xylene enables a fluid reaction system to be realized. The reaction is effected under substantially anhydrous conditions. In order to insure completion of the reaction after addition of the chloroester, the reaction mixture is heated within the indicated temperature range for a reasonable time. The formed phosphate is usually recovered by distillation under sutficiently low pressure that thermal decomposition is avoided. If desired, especially with higher compounds of the invention, crystallization or molecular distillation may be used for recovery of the phosphates.
An alternative, and in many cases more convenient route to the products of the invention is by substituting for Reaction a, the reaction of diketene or substituted diketenes with the alcohols to form the corresponding beta-0x0 fatty acid ester, i.e.
l I ROH or (R R OH R CH-C=O a The reaction is catalyzed by acidic or basic catalysts, such as acid or basic resins, tertiary amines, or sulfonic acids. The reaction is conveniently effected by heating a mixture of approximately equimolar portions of the diketene and the alcohol, together with a catalytic amount of the catalyst, to a moderately elevated temperature (100 C. to 150 C. is usually most satisfactory) for a suflicient time to complete the reaction. If a resin is used as catalyst it is then removed by filtration, and the product obtained by distillation of the filtrate. If an amine or sulfonic acid is used as catalyst, it may be removed by neutralization and/or washing the reaction mixture with water, followed by drying of the product and removal of the solvent. This reaction is illustrated by the following example:
EXAMPLE I Reaction of an alcohol with diketene 2-acetoxyethyl acetoacetate is prepared by mixing diketene (42 grams-05 mole) and 2-hydroxyethyl acetate (52 grams0.5 mole) together with 1 gram of a sulfonic acid ion exchange resin (Amberlite IR-120, acid form) and heating carefully at to C. for approximately 1 hour. The resin is removed by filtration.
; The product then is obtained by fractionating this filtrate ina vacuum; Yield 32.5 grams (35% of theory); B.P. 90-101" C. (approx. 0.1 mm); n D 1.4390; d='1.18.
Analysis oi Analysis Product Calculated tor CsHnOs 52. 2 Hydrogen, percent w 6. 2
EXAMPLE II 2-(2-acetoxyethoxycarbonyl)-1 methylvinyl dimethyl phosphate is prepared by adding trimethyl phosphite (136.6 grams-4.1 moles) to 2-acetoxyethyl 2-chloroacetoacetate 189 grams-0.85 mole) over a period of 1.5 hours. The reaction is moderately exothermic and the temperature is maintained at 70 C. during the addition by adjusting the rate of addition 'of the trimethyl phosphite. At the end of the addition the reaction mixture is heated for 2 hours at 120C. at atmospheric pressure and then for 2 hours at 100 "C. at approximately 20 mm. pressure in order to remove the by-product methyl chloride and excess trimethyl phosphite. isolated by distilling in a'Claisen apparatus, is obtained as a water white slightly viscous liquid. Yield 190 grams (75.5% of theory). B.P. 1557 C. (0.08 mm); n D 1.4580; d=1.23.
Analysis of .Product Analysis Calculated for POgCmHi'! Carbon, percent W 38 Hydrogen, percent w 1g EXAMPLE III 2-(Z-acetoxyethoxycarbonyl) 1.- methylvinyl diethyl phosphate is made by adding tn'ethylphosphite (33.2 grams-0.20 mole) to 2-acetoxyethy1 2-chloroacetoacetate (44.5 grams0.20 mole) over aperiod of /2 hour. The reaction is exothermic and the temperature is maintained at 100 C. by adjusting the rate ofaddition. At the end of the addition heat is applied to maintain temperature at 100 C. for 95 hour while a vacuum of 130 mm. is maintained to remove the by-product ethyl chloride. The product is isolated by a high vacuum distillation (molecular still) as a water-white slightly viscous liquid. Yield 60 grams (92.5% of theory) .B.P. 150 C. (0.001 mm); n D 1.4533; d=1.2.
Analysis Calculated forPOsCuH Analysis of Product Carbon, percent w 44. 7 Hydrogen, percent w 18.8
4%. Phosphorus, percent w -9:
ODOIUI EXAMPLE 91V y i Calculated for POaClsHra Analysis of Product Carbon, percent w Hydrogen, percent w Phosphorus, percent w The product,
chloride.
'6 EXAMPLE V 2-(2-methoxyethoxy) carbonyl-'l-methylvinyl dimethyl phosphate is prepared by adding trimethyl phosphite (25 grams0.20 mole) to 2-methoxyethyl 2-ch1oroacetoacetate (39 grams-020 mole) at to C. over V2 hour period. The reaction is mildly exothermic and the temperature is maintained at 85 to 90 C. by adjusting the rate of addition. After completion of the addition heat is applied for 1 hour at 85 to 90 C. at atmospheric pressure and then for /2 hour at 115 C. and 0.1 mm. pressure to remove the by-product methyl The product is obtained by distilling in a high vacuum (molecular still). Yield 36.5 grams (68% of theory); B.P. C. (0.001 mm.); n D 1.4537; d==1.22.
EXAMPLE VI Diethyl 2-(Z-methoxyethoxycarbonyl) 1 methylvinyl phosphate is prepared by adding triethyl phosphite (16.6 grams-0.1 mole) to 2-methoxyethyl 2-chloroacetoacetate over a period of 4 hour. The heat of reaction gives a reaction temperature of 80 C. At the end of the addition, the mixture is heated for 1 hour at 80 to 90 C. and then for 2 hours at 80 to 100 C. and 120 mm. pressure-to remove the by-product ethyl chloride. The product is isolated by distilling this crude product in a high vacuum (molecular still). Yield 21.1 grams (71.4% of theory); B.P. C. (0.001 mm.); :1 D 1.4497; d=1.14.
Z-carbethoxy-l-methylvinyl ethyl Z-methoxyethyl phosphate is prepared by adding diethyl 2-methoxyethyl phosphate (50.3 grams0.26 mole) to ethyl Z-chloroacetoacetate (42.2 grams0.26 mole) at 80 to 105 C. over a period. of /2 hour. Although the reaction is slightly exothermic, heat is applied during the addition tomaintain the reaction temperature. At the end of the addition heating is continued at 105 C. and 25 mm. pressure for /2 hour to remove theby-product ethyl chloride. The product is isolated by fractionation in a high vacuum (molecular still). Yield 50.5 grams (66.5% of theory); Bl. C. (0.001 mm.); n D 1.4481; d=1.15.
Bis(2-methoxyethyl) 2-(Z-methoxyethoxycarbonyl)-1- methylvinyl phosphate is prepared by adding tris(2- methoxyethyl) phosphite (38.6 grams-0.15 mole) to 2-methoxyethyl Z-chloroacetoacetate (29.2 grams0.15 mole) at 100C. over a A hour period. Heat is applied =to-maintain the reaction temperature at 100 "C.
Analysis of Analysis Product Calculated for P01012112:
Carbon, percent w. 42. 2 43. 8 Hydrogen, percent w 6. 2 7. Phosphorus, percent w 8. 8 8. 7
Other members of the new class of esters are in a similar manner.
Many of the complex esters of the invention are liquids at ordinary temperatures of C. to C. although higher members are crystalline solids at such normal temperatures. The new compounds are very useful substances for a variety of applications but are of particular utility as insecticides because they possess outstanding properties when employed ascontact and stomach poi sons. The compounds are highly toxic to insects, a term which is employed herein to include not only members of the class Insecta, but also related or similar non-vertebrate animal organisms belonging to the allied classes of arthropods and including mites, ticks, spiders, wood lice, and the like.
The compounds of this invention can be employed for insecticidal purposes by the use of any of the methods which are conventionally employed in that art. For example, the compounds can either be sprayed or otherwise applied in the form of a solution or dispersion, or
it can be absorbed on an inert, finely-divided solid and applied as a dust. Useful solutions for. application by spraying, brushing, dipping, and the like, can be prepared by using as the solvent any of the well-known inert horticultural carriers, including neutral hydrocarbons such as kerosene and other light mineral oil distillates of intermediate viscosity and volatility. Adjuvants, such as spreading or wetting agents, can also be included in the solutions, representative materials of'this character being fatty acid soaps, rosin 'salts, saponins,' gelatin, casein, long-chain fatty alcohols, alkyl aryl sulfonates, long-chain alkyl sulfonates, phenolethylene oxide condensates, ammonium salts, and the like. These solutions can be employed as such, or, more preferably, they can be dispersed or emulsified'in' water and the resulting aqueous dispersion or emulsion applied as a spray. Solid carrier materials which can be employed include talc, bentonite, lime, gypsum, pyrophyllite andsimilar inert solid ,dilu'ents. If desired, the compounds of the present invention can be employed as aerosols, as by dispersing the same into the atmosphere by means of a compressed The concentration of the compounds to be used with the above carriers is dependent upon many factors, including the particular compound utilized, the can'ier employed, the method and conditions of application, and the insect speciesto be controlled, a proper consideration and resolution of these factors being within the skill of those versed in the insecticide art. In general, however, the compounds of this invention are effective in concentrations of from about 0.01% to 0.5% based upon the total weight of the composition, though under some circumstances as little as about 0.00001% or as much as 2% or even more of the compound can be employed with good results from an'in'secticidal standpoint.
When employed as an insecticide, a compound of this invention can be employed either as the: sole toxic ingredient of the insecticidal composition or can be employed in conjunction with otherinsecticidallkactive materials. Representative insecticides of this latter class include the natura yoc unin i se cides such as. .py-
prepared rethrum, rotenone, sabadilla, and the like, as well as the various synthetic insecticides, including DDT, benzene hexachloride, thiodiphenylamine, cyanides, tetraethyl pyrophosphate, diethyl-p-nitrophenyl thiophosphate, azobenzene, and the various compounds of arsenic, lead, and/ or fluorine.
The following examples demonstrate the insecticidal qualities of typical compounds of this invention with a comparison being made between the properties of these esters and those of various compounds widely used as insecticides.
' EXAMPLE IX The toxicity of representative products of the invention against the common housefly (Musca domestica) was determined using the method described by Y. P. Sun, Journal of Economic Entomology, volume 43, page 45 et seq. (1950). The toxicities were compared to that of alpha-chlordane. The toxicities are expressed in terms of the relationship between the amount of alpha-chlordane required to produce 50% mortality of the test insects and the amount of the test material required to produce the same mortality. Assigning alphachlordane an arbitrary rating of the toxicity of the test materials is expressed in terms of the toxicity index which compares the activity on a percentage basis with that of the alphachlordane. The results are shown in the following table:
EXAMPLE X In furthertests, representative compounds of the invention were tested against other common insect pests, comparison being made to common insecticides widely used'against such pests. Solutions or emulsions of the representative compounds were made up by employing acetone, or a neutral petroleum distillate lying within the kerosense range as the solvent. These solutions or emulsions were tested for toxicity against (a) the two-spotted spider mite (T etranychus bimaculatus), (b) the pea aphid (Macrosiphum pisi), (c) the Mexican bean beetle larva (Epilachna varivestis), (d) the southern armyworm (Prodenia eridania), (e) the black bean aphid (Aphis fabae), f) the green peach aphid (Myzus persicae), (g) the cotton aphid (Aphis gossypii) and (h) the hydrangea mite (Tetranychus hydrangea), by spraying groups of plantsfinfested with the insects under controlled conditions which varied from test to test only in the identity of the'tox'ic agent audits concentration. These toxicities were compared with the toxicity of (a) parathion, (b) nicotine, (c) the gammaisomer of hexachlorobenzene, (d) DDT, (e) a-chlordane and (f) dieldrin, all insecticides widely used for the destruction of the common insects tested. In each set of tests the conditions were directly comparable-i.e., the same test insect, same plant, environment, etc, were used and the concentration of active material in each case was the same. The toxicities of the test compounds are expressed in terms of a toxicity index, this index being determined as set out in Example villl. The results .of the testsare set out in the following ta e.
Table II.. -Toxicity index (standard=100) House Mexican Bean Southern Army Two- Black Green Hydran- Test Insect; Fly Pea aphid Beetle Larva Worm spotted Bean Peach Cotton gea Spider, Aphid Aphid Aphid Mite Mite Gamma Standard aghlor Nicotine Parathion Bfinzene' Parathlon DDT Dieldrin Parathion Parathion Parathion Parathion Parathlon ane exaa chloride Compound:
1, 3&0 6, 630 '180 1, 800 170 460 590 135 165 940 A 2-(Z-methoxyethoxycarbonyl) l-methylvlnyl dlmethyl phosphate. B=2-(2-acetoxyethoxycarbonyl)-l-rnethylvinyl dlmethyl phosphate.
O=2- 2acetoxye'thoxyc'arbony1)-1-methy1vlnyl dlethyl phosphate;
D=2- 2-(benzoyloxy)ethoxycarbonyl]-1-methylvinyl dlmethyl phosphate. E=2-carbethoxy-1-methylvinyl ethyl 2-methoxyethyl phosphate. F=2-(2-methoxyethoxycarbonyl)-1-methylvinyl diethyl phosphate. G=Bls-(2-methoxyethyl) 2-(2-methoxyeth0xyoarbonyl)-1methylviny1 phosphate.
EXAMPLE XI Table V [Test insect: Adult two-spotted spider mite.]
Certain representative compounds of the invention were tested to determine their residual toxicity with respect Percent control to the adults of several common insects. These tests were pe'rfiormediby spraying the unifested test plants with the Concentration of active materialinspray.-. 1.0% w. 0.25% w. test compound as set out in Example IX, and a given I y p j number of days thereafter infesting the plantswith the Time (infestation after spraying, days) 1 7 1 7 testinsects. The effectiveness of the test compound is expressed as the percent of the test insects (compared to oomnzund i m 100 100 99 51 S68 8, e c.
untreated but equally infested test plants). the count D (See Table I m0 100 100 100 being made 24 hours after the mfestatlon. The details of Parathion (for comparison) 99 62 97 36 the tests and the results thereof are summarized in the I p a following tables: Table VI [Test insect: Mexican bean beetle larva. Time of infestation: 7 days T l III after spraying. (The concentration of test compound in the spray is given in parentheses following the percent kill, in the table.)]
[Test insect: onion thrips (Thn'ps tabaci)] 40 Percent kill Percent control 7 Concentration of Condition In shade In sun active Material in spray %oz./100 gal. 3 ozJ/IOO gal. 6 oz./100 gal. oompound A Time (infestation g" f fff 1 7 1 7 1 7 Paratliion (for comparison Corn ound'tes D see Table-II) 83 .52 84 81 93 .84 n) 69 '42 80 641 90 60 Tests were also made on certain of the compounds of the invention, Parathion, Systox and dimcthyl l-carbo- Table IV methoxy-l-propen-Z-yl phosphate, another known insecticide under conditions such that the residual toxicity [Test insect: hydrangea mite. Test compound: D (see vTable .II). of the compounds toward the eggs, the Young hatched Concentration ractive'mater a in spr i 0 g -l from the eggs, as well as the adults of two-spotted spider mites, would be measured. The time of infestation was Time (infestation after spraying, -deys)... 1 2 7 7 days after spraying. The results are shown in the folr lowing table. (In the table, the concentration of the Percent n 100 100 78 test compound in the spray is given in parentheses following the percent kill.)
Table VII Percent kill Compound:
11 EXAMPLE XIII A representative member of the new class of insecticides also as tested under conditions such that the residual toxicity thereof would be determined. For comparison, Systox, Parathion, and dimethyl l-carbomethoxy-lpropen-2-yl phosphate, were tested under the same conditions.
The tests were conducted against leafhoppers (Erythroneura comes) on grapes. Iindividual grape canes were sprayed to run-01f with 3 ounces actual toxicant per 100 gallons of water. The sprays were then repeated two more times. Twenty-five adult leafhoppers were caged on each cane at intervals after each spray and counts were made 24 hours later. results obtained are given in Table VIII.
Table VIII Percent control (average) Time (days following iniestation after spray- Compound: B (see Table II) Systmr Parnthinn Dimethyl l-carb m etho xy-1-propen-2-yl phosphate A summary of the 5. 2 (2 methoxyethoxycarbonyl) l methylvinyl diethyl phosphate.
6. 2 carbethoxy 1 methylvinyl ethyl 2 methoxyethyl phosphate.
7. A compound of the formula wherein R represents a member of the group consisting of hydrogen and alkyl radicals of 1 to 8 carbon atoms,
R represents an alkyl radical of 1 to 8 carbon atoms, R represents an alkylene group of not more than 10 carbon atoms, R represents a functional group involving oxygen of not more than 10 carbon atoms selected from the group consisting of -0R and wherein R represents a member of the group consisting of hydrogen and alkyl radicals of 1 to 8 carbon- 12 atoms, R represents an alkyl radical of 1 to 8 carbon atoms, R 'represents an alkylene group of not more than 10 carbon atoms, and R represents a functional group involving oxygen of not more than 10 carbon atoms selected from the group consisting of OR and wherein R is an alkyl radical.
9. A compound of the formula wherein R represents a member of the group consisting of hydrogen and alkyl groups of 1 to 8 carbon atoms, R represents an alkyl radical of 1 to 8 carbon atoms, R represents an alkylene group of not more than 10 carbon atoms, R represents a functional group involving oxygen of not more than 10 carbon atoms selected from the group consisting of --OR and wherein R is an alkyl radical.
11. A compound of the formula wherein R represents a member of the groupconsisting of hydrogen and alkyl radicals to 1 to 8 carbon atoms, R represents an alkyl radical of 1 to 8 carbon atoms, R3 represents an alkylene group of not more than 10 carbon atoms, R represents a functional group involving oxygen having not more than 10 carbon atoms selected from the group consisting of OR and wherein R is an alkyl radical, a represents an integer selected from the group consisting of 0, 1 and 2, with the provision that a+b=2, and c is an integer selected from the group consisting of 0 and 1, with the provision that c+d=1, and with the further provision that b+d=at least 1.
References Cited in the file of this patent UNITED STATES PATENTS Stiles Aug. 3, 1954 Norman et al Aug. 13, 1957
Claims (1)
11. A COMPOUND OF THE FORMULA WHEREIN R'' REPRESENTS A MEMBER OF THE GROUP CONSISTING OF HYDROGEN AND ALKYL RADICALS TO 1 TO 8 CARBON ATOMS, R REPRESENTS AN ALKYL RADICAL OF 1 TO 8 CARBON ATOMS, R2 REPRESENTS AN ALKYLENE GROUP OF NOT MORE THAN 10 CARBON ATOMS R3 REPRESENTS A FUNCTIONAL GROUP INVOLVING OXYGEN HAVING NOT MORE THAN 10 CARBON ATOMS SELECTED FROM THE GROUP CONSISTING OF -OR4 AND
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US555753A US2894014A (en) | 1955-12-28 | 1955-12-28 | Complex esters of beta-phosphato-alpha, beta-olefinically unsaturated monocarboxylic acids |
DEN13116A DE1149939B (en) | 1955-12-28 | 1956-12-21 | Insect repellants |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US555753A US2894014A (en) | 1955-12-28 | 1955-12-28 | Complex esters of beta-phosphato-alpha, beta-olefinically unsaturated monocarboxylic acids |
Publications (1)
Publication Number | Publication Date |
---|---|
US2894014A true US2894014A (en) | 1959-07-07 |
Family
ID=24218465
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US555753A Expired - Lifetime US2894014A (en) | 1955-12-28 | 1955-12-28 | Complex esters of beta-phosphato-alpha, beta-olefinically unsaturated monocarboxylic acids |
Country Status (2)
Country | Link |
---|---|
US (1) | US2894014A (en) |
DE (1) | DE1149939B (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3053729A (en) * | 1959-10-26 | 1962-09-11 | Shell Oil Co | Insecticidal compositions |
US3059014A (en) * | 1958-06-06 | 1962-10-16 | Monsanto Chemicals | Process for preparing organic compounds of phosphorus and sulfur |
US3068268A (en) * | 1961-02-13 | 1962-12-11 | Shell Oil Co | Preparation of vinyl esters of phosphorus acids useful as insecticides |
US3081220A (en) * | 1960-05-23 | 1963-03-12 | Shell Oil Co | Fungicidal process |
US3093536A (en) * | 1961-04-05 | 1963-06-11 | Shell Oil Co | Stabilized halogenated enol ester pesticidal compositions |
US3097128A (en) * | 1961-01-06 | 1963-07-09 | Shell Oil Co | Phenol stabilized organo-phosphorous insecticides |
US3136686A (en) * | 1958-10-31 | 1964-06-09 | Ciba Ltd | Omicron, omicron-dialkyl s-alkenyl phosphorothioates and insecticidal compositions and methods employing same |
US4101432A (en) * | 1977-07-14 | 1978-07-18 | Mobil Oil Corporation | Lubricant compositions containing organophosphorus derivatives of hydroxycarboxylic acids |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE580528A (en) * | 1958-07-10 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2685552A (en) * | 1952-02-29 | 1954-08-03 | Shell Dev | Dimethyl 1-carbomethoxy-1-propen-2-yl phosphate |
US2802856A (en) * | 1953-09-08 | 1957-08-13 | Lubrizol Corp | Methods of preparing tri-esters of thiophosphoric acids |
-
1955
- 1955-12-28 US US555753A patent/US2894014A/en not_active Expired - Lifetime
-
1956
- 1956-12-21 DE DEN13116A patent/DE1149939B/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2685552A (en) * | 1952-02-29 | 1954-08-03 | Shell Dev | Dimethyl 1-carbomethoxy-1-propen-2-yl phosphate |
US2802856A (en) * | 1953-09-08 | 1957-08-13 | Lubrizol Corp | Methods of preparing tri-esters of thiophosphoric acids |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3059014A (en) * | 1958-06-06 | 1962-10-16 | Monsanto Chemicals | Process for preparing organic compounds of phosphorus and sulfur |
US3136686A (en) * | 1958-10-31 | 1964-06-09 | Ciba Ltd | Omicron, omicron-dialkyl s-alkenyl phosphorothioates and insecticidal compositions and methods employing same |
US3053729A (en) * | 1959-10-26 | 1962-09-11 | Shell Oil Co | Insecticidal compositions |
US3081220A (en) * | 1960-05-23 | 1963-03-12 | Shell Oil Co | Fungicidal process |
US3097128A (en) * | 1961-01-06 | 1963-07-09 | Shell Oil Co | Phenol stabilized organo-phosphorous insecticides |
US3068268A (en) * | 1961-02-13 | 1962-12-11 | Shell Oil Co | Preparation of vinyl esters of phosphorus acids useful as insecticides |
US3093536A (en) * | 1961-04-05 | 1963-06-11 | Shell Oil Co | Stabilized halogenated enol ester pesticidal compositions |
US4101432A (en) * | 1977-07-14 | 1978-07-18 | Mobil Oil Corporation | Lubricant compositions containing organophosphorus derivatives of hydroxycarboxylic acids |
Also Published As
Publication number | Publication date |
---|---|
DE1149939B (en) | 1963-06-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2956073A (en) | Insecticidally active esters of phosphorus acids and preparation of the same | |
US3116201A (en) | Organo-phosphorus insecticide | |
US2744128A (en) | Olefinically unsaturated phosphates | |
US2685552A (en) | Dimethyl 1-carbomethoxy-1-propen-2-yl phosphate | |
US2802855A (en) | Carbamylalkenyl phosphoruscontaining esters | |
US2894014A (en) | Complex esters of beta-phosphato-alpha, beta-olefinically unsaturated monocarboxylic acids | |
US2908605A (en) | New organic phosphorus compounds and process for their manufacture | |
US2765331A (en) | Esters of phosphorus acids and process for the preparation of the same | |
US3027296A (en) | Halogenated phosphorus esters | |
US2861912A (en) | Method for combating pests and preparations suitable therefor | |
DE1214228B (en) | Process for the production of organic phosphorus compounds | |
US2895982A (en) | Complex nitrophenyl phosphates | |
US2865944A (en) | Complex amido-substituted esters of beta-phosphato-alpha, beta-olefinically unsaturated monocarboxylic acids | |
US2931755A (en) | Omicron, omicron-dialkyl or omicron, omicron-bis (haloalkyl) s-dichloromethyl phosphorothioates | |
US2867646A (en) | Complex arylphosphonates | |
US2909544A (en) | Organic phosphorus complex | |
US2663722A (en) | Method of preparing tetraalkyl dithionopyrophosphates | |
US3555123A (en) | Di-omega-alkynyl aryl(arylalkyl) phosphonates | |
US3166581A (en) | S-acyloxyalkyl and s-acyloxyalkenyl esters of o, o-diorgano-phosphorothiolic acids | |
US3136784A (en) | Beta-phosphate esters of -2-butenoates of mono glyceriate heterocyclic acetals and glyceriate carbonates | |
US3189635A (en) | Dialkyl 1, 2-disubstituted-ethylphosphonates and their preparation | |
US2912450A (en) | Reaction products of dialkyl phosphorothiolothionates and acetylenic compounds | |
US2787629A (en) | Bis (chloromethane alkyl) phosphonic acid anhydrides | |
US3053852A (en) | Phosphorothiolothionates derived from vinylene carbonate and vinylene sulfite | |
US2995486A (en) | Method for combating pests and preparations suitable therefor |